Aromatic amine derivative, and organic electroluminescent element comprising the same

ABSTRACT

An aromatic amine derivative represented by the following formula (1) 
     wherein at least one of Ar 1  to Ar 4  is a heterocyclic group represented by the following formula (2) wherein X 1  is an oxygen atom or a sulfur atom.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a Continuation of U.S. application Ser. No.13/773,203, filed Feb. 21, 2013, which is a Continuation of U.S.application Ser. No. 13/138,750 based upon PCT National StageApplication No. PCT/JP2010/002959 filed Sep. 23, 2011, and claims thebenefit of priority from prior Japanese Patent Application No.2009-105963, filed Apr. 24, 2009 and Japanese Patent Application No.2009-195976, filed Aug. 26, 2009, the entire contents of each of theseapplications are incorporated herein by reference.

TECHNICAL FIELD

The invention relates to an aromatic amine derivative and an organicelectroluminescence device using the same. In particular, the inventionrelates to an organic electroluminescence device having a long life, ahigh luminous efficiency and a high chromatic purity and an aromaticamine derivative realizing the same.

BACKGROUND ART

An organic electroluminescence (EL) device using an organic material isa promising solid-state emitting type inexpensive and large full-colordisplay device, and has been extensively developed. In general, anorganic EL device includes an emitting layer and a pair of opposingelectrodes holding the emitting layer therebetween. Emission is aphenomenon in which when an electric field is applied between theelectrodes, electrons are injected from the cathode and holes areinjected from the anode, the electrons recombine with the holes in theemitting layer to produce an excited state, and energy is emitted aslight when the excited state returns to the ground state.

Conventional organic EL devices have a higher driving voltage than aninorganic light-emitting diode. The luminance or luminous efficiencythereof is also low, and their properties tend to deterioratesignificantly. For these reasons, conventional organic EL devices havenot been put in a practical use. Although recent organic EL devices havebeen improved gradually, further improvement in luminous efficiency,prolongation in life time, color reproducibility or the like has beendemanded.

The performance of an organic EL device has been improved gradually byimproving an emitting material for an organic EL. In particular,improvement in chromatic purity of a blue-emitting organic EL device(shortening of the emission wavelength) is an important technology whichleads to improvement in color reproducibility of a display.

As the example of a material used in an emitting layer, Patent Document1 discloses an emitting material having dibenzofuran. This emittingmaterial is capable of emitting blue light having a short wavelength.However, an organic EL device using this emitting material has a poorluminous efficiency, and hence, further improvement has been desired.

Patent Documents 4 and 5 each disclose a diaminopyrene derivative.Patent Document 2 discloses a combination of an anthracene host and anarylamine. Patent Documents 3 to 5 disclose a combination of ananthracene host with a specific structure and a diaminopyrene dopant.Further, Patent Documents 6 to 8 disclose an anthracene-based hostmaterial.

In each material and in each combination, although it can be admittedthat emission properties are improved, emission properties are not yetsufficient. Under such circumstances, an emitting material capable ofrealizing a high luminous efficiency and capable of emitting light at afurther shorter wavelength has been demanded.

Patent Document 9 discloses the use of an aromatic amine derivativewhich has an arylene group at the central thereof and in which adibenzofuran ring is bonded to a nitrogen atom as the hole-transportingmaterial. Patent Document 10 discloses the use of an aromatic aminederivate in which a dibenzofuran ring, dibenzothiophen ring, abenzofuran ring, a benzothiophen ring or the like is bonded to anitrogen atom through an arylene group as a hole-transporting material.However, no example is given in which this aromatic amine derivative isused as an emitting material.

RELATED ART DOCUMENTS Patent Documents

[Patent Document 1] WO2006/128800

[Patent Document 2] WO2004/018588

[Patent Document 3] WO2004/018587

[Patent Document 4] JP-A-2004-204238

[Patent Document 5] WO2005/108348

[Patent Document 6] WO2005/054162

[Patent Document 7] WO2005/061656

[Patent Document 8] WO2002/038524

[Patent Document 9] JP-A-H11-35532

[Patent Document 10] WO2007/125714

SUMMARY OF THE INVENTION

The invention is aimed at providing an organic EL device capable ofemitting blue light with a high chromatic purity at a high luminousefficiency and a material which can be used in organic thin film layersof the organic EL device.

According to the invention, the following aromatic amine derivative andthe organic electroluminescence device can be provided.

1. An aromatic amine derivative represented by the following formula(1):

wherein R₁ to R₈ are independently a hydrogen atom, a halogen atom, asubstituted or unsubstituted alkyl group having 1 to 20 carbon atoms, asubstituted or unsubstituted cycloalkyl group having 3 to 10 ring carbonatoms, a substituted or unsubstituted silyl group, a cyano group or asubstituted or unsubstituted aryl group having 6 to 30 carbon atoms thatform a ring (hereinafter referred to as “ring carbon atoms”), and

Ar₁ to Ar₄ are independently a substituted or unsubstituted aryl grouphaving 6 to 30 ring carbon atoms or a substituted or unsubstitutedheterocyclic group having 5 to 30 atoms that form a ring (hereinafterreferred to as the “ring atoms”),

provided that at least one of Ar₁ to Ar₄ is a heterocyclic grouprepresented by the following formula (2):

wherein R₁₁ to R₁₇ are independently a hydrogen atom, a halogen atom, asubstituted or unsubstituted alkyl group having 1 to 20 carbon atoms, asubstituted or unsubstituted alkenyl group having 2 to 20 carbon atoms,a substituted or unsubstituted alkynyl group having 2 to 20 carbonatoms, a substituted or unsubstituted silyl group, a cyano group, asubstituted or unsubstituted aryl group having 6 to 20 ring carbon atomsor a substituted or unsubstituted heterocyclic group having 5 to 20 ringatoms,

adjacent substituents of R₁₁ to R₁₇ may be bonded to form a saturated orunsaturated ring, and

X₁ is an oxygen atom or a sulfur atom.

2. The aromatic amine derivative according to 1 which is represented bythe following formula (3):

wherein R₁ to R₈, Ar₂ and Ar₄ are the same as those in formula (1),

R₂₁ to R₂₇ and R₃₁ to R₃₇ are independently a hydrogen atom, a halogenatom, a substituted or unsubstituted alkyl group having 1 to 20 carbonatoms, a substituted or unsubstituted alkenyl group having 2 to 20carbon atoms, a substituted or unsubstituted alkynyl group having 2 to20 carbon atoms, a substituted or unsubstituted silyl group, a cyanogroup, a substituted or unsubstituted aryl group having 6 to 20 ringcarbon atoms or a substituted or unsubstituted heterocyclic group having5 to 20 ring atoms,

adjacent substituents of R₂₁ to R₂₇ and R₃₁ to R₃₇ may be bonded to forma saturated or unsaturated ring, and

X₂ and X₃ are independently an oxygen atom or a sulfur atom.

3. The aromatic amine derivative according to 2 wherein Ar₂ and Ar₄ area heterocyclic group represented by the following formula (4):

wherein one of R₄₁ to R₄₈ is used for connection to the nitrogen atom,and the other substituents are independently a hydrogen atom, a halogenatom, a substituted or unsubstituted alkyl group having 1 to 20 carbonatoms, a substituted or unsubstituted alkenyl group having 2 to 20carbon atoms, a substituted or unsubstituted alkynyl group having 2 to20 carbon atoms, a substituted or unsubstituted silyl group, a cyanogroup, a substituted or unsubstituted aryl group having 6 to 20 ringcarbon atoms or a substituted or unsubstituted heterocyclic group having5 to 20 ring atoms, adjacent substituents of R₄₁ to R₄₈ may be bonded toform a saturated or unsaturated ring, and X₄ is an oxygen atom or asulfur atom.4. The aromatic amine derivative according to any one of 1 to 3 whereinR₁ to R₈ are a hydrogen atom.5. The aromatic amine derivative according to any one of 1 to 3 whereinR₂ is a substituted or unsubstituted alkyl group having 1 to 20 carbonatoms, a substituted or unsubstituted cycloalkyl group having 3 to 10ring carbon atoms, a substituted or unsubstituted silyl group, or asubstituted or unsubstituted aryl group having 6 to 30 ring carbonatoms, and R₁ and R₃ to R₈ are a hydrogen atom.6. The aromatic amine derivative according to any one of 1 to 3 whereinR₂ and R₆ are a substituted or unsubstituted alkyl group having 1 to 20carbon atoms, a substituted or unsubstituted cycloalkyl group having 3to 10 ring carbon atoms, a substituted or unsubstituted silyl group, ora substituted or unsubstituted aryl group having 6 to 30 ring carbonatoms, and R₁, R₃, R₄, R₅, R₇ and R₈ are a hydrogen atom.7. The aromatic amine derivative according to any one of 1 to 6 whereinX₁, X₂, X₃ and X₄ are an oxygen atom.8. The aromatic amine derivative according to any one of 1 to 7 which isan emitting material for an organic electroluminescence device.9. The aromatic amine derivative according to any one of 1 to 8 which isa doping material for an organic electroluminescence device.10. An organic electroluminescence device comprising one or more organicthin film layers comprising an emitting layer between an anode and acathode,

wherein at least one layer of the organic thin film layers comprises thearomatic amine derivative according to any one of 1 to 9 singly or as acomponent of a mixture.

11. The organic electroluminescence device according to 10, wherein theat least one layer is an emitting layer.12. The organic electroluminescence device according to 10, wherein theat least one layer comprises the aromatic amine derivative according toany one of 1 to 9 and an anthracene derivative represented by thefollowing formula (5):

wherein Ar¹¹ and Ar¹² are independently a substituted or unsubstitutedmonocyclic group having 5 to 50 ring atoms, a substituted orunsubstituted fused ring group having 8 to 50 ring atoms, or a groupformed by combination of the monocyclic group and the fused ring groupand

R¹⁰¹ to R¹⁰⁸ are independently a group selected from a hydrogen atom, asubstituted or unsubstituted monocyclic group having 5 to 50 ring atoms,a substituted or unsubstituted fused ring group having 8 to 50 ringatoms, a group formed by combination of the monocyclic group and thefused ring group, a substituted or unsubstituted alkyl group having 1 to50 carbon atoms, a substituted or unsubstituted cycloalkyl group having3 to 50 ring carbon atoms, a substituted or unsubstituted alkoxy grouphaving 1 to 50 carbon atoms, a substituted or unsubstituted aralkylgroup having 7 to 50 carbon atoms, a substituted or unsubstitutedaryloxy group having 6 to 50 ring carbon atoms, a substituted orunsubstituted silyl group, a halogen atom and a cyano group.

13. The organic electroluminescence device according to 12 wherein informula (5), Ar¹¹ and Ar¹² are independently a substituted orunsubstituted fused ring group having 10 to 50 ring carbon atoms.14. The organic electroluminescence device according to 12 wherein informula (5), one of Ar¹¹ and Ar¹² is a substituted or unsubstitutedmonocyclic group having 5 to 50 ring atoms, and the other is asubstituted or unsubstituted fused ring group having 8 to 50 ring atoms.15. The organic electroluminescence device according to 14 wherein informula (5), Ar¹² is a naphthyl group, a phenanthryl group, abenzanthryl group or a dibenzofuranyl group, and Ar¹¹ is a phenyl groupwhich is unsubstituted or substituted by a monocyclic group or fusedring group.16. The organic electroluminescence device according to 14 wherein informula (5), Ar¹² is a substituted or unsubstituted fused ring grouphaving 8 to 50 ring atoms, and Ar¹¹ is an unsubstituted phenyl group.17. The organic electroluminescence device according to 12 wherein informula (5), Ar¹¹ and Ar¹² are independently a substituted orunsubstituted monocyclic group having 5 to 50 ring atoms.18. The organic electroluminescence device according to 17 wherein informula (5), Ar¹¹ and Ar¹² are independently a substituted orunsubstituted phenyl group.19. The organic electroluminescence device according to 18 wherein informula (5), Ar¹¹ is an unsubstituted phenyl group and Ar¹² is a phenylgroup having a monocyclic group or a fused ring group as a substituent.20. The organic electroluminescence device according to 18 wherein informula (5), Ar¹¹ and Ar¹² are independently a phenyl group having amonocyclic group or a fused ring group as a substituent.

According to the invention, an organic EL device capable of emittingblue light with a high chromatic purity at a high luminous efficiency,and a material which can be used for organic thin film layers of theorganic EL device can be provided.

MODE FOR CARRYING OUT THE INVENTION

The aromatic amine derivative of the invention is represented by thefollowing formula (1):

In the formula (1), R₁ to R₈ are independently a hydrogen atom, ahalogen atom, a substituted or unsubstituted alkyl group having 1 to 20carbon atoms, a substituted or unsubstituted cycloalkyl group having 3to 10 ring carbon atoms, a substituted or unsubstituted silyl group, acyano group or a substituted or unsubstituted aryl group having 6 to 30carbon atoms, and

Ar₁ to Ar₄ are independently a substituted or unsubstituted aryl grouphaving 6 to 30 ring carbon atoms or a substituted or unsubstitutedheterocyclic group having 5 to 30 ring atoms,

provided that at least one of Ar₁ to Ar₄ is a heterocyclic grouprepresented by the following formula (2):

In the formula (2), R₁₁ to R₁₇ are independently a hydrogen atom, ahalogen atom, a substituted or unsubstituted alkyl group having 1 to 20carbon atoms, a substituted or unsubstituted alkenyl group having 2 to20 carbon atoms, a substituted or unsubstituted alkynyl group having 2to 20 carbon atoms, a substituted or unsubstituted silyl group, a cyanogroup, a substituted or unsubstituted aryl group having 6 to 20 ringcarbon atoms or a substituted or unsubstituted heterocyclic group having5 to 20 ring atoms,

adjacent substituents of R₁₁ to R₁₇ may be bonded to form a saturated orunsaturated ring, and

X₁ is an oxygen atom or a sulfur atom.

The aromatic amine derivative is preferably represented by the followingformula (3):

In the formula (3), R₁ to R₈ and Ar₂ and Ar₄ are the same as those inthe formula (1),

R₂₁ to R₂₇ and R₃₁ to R₃₇ are independently a hydrogen atom, a halogenatom, a substituted or unsubstituted alkyl group having 1 to 20 carbonatoms, a substituted or unsubstituted alkenyl group having 2 to 20carbon atoms, a substituted or unsubstituted alkynyl group having 2 to20 carbon atoms, a substituted or unsubstituted silyl group, a cyanogroup, a substituted or unsubstituted aryl group having 6 to 20 ringcarbon atoms, or a substituted or unsubstituted heterocyclic grouphaving 5 to 20 ring atoms, adjacent substituents of R₂₁ to R₂₇ and R₃₁to R₃₇ may form a saturated or unsaturated ring, and

X₂ and X₃ are independently an oxygen atom or a sulfur atom.

It is preferred that, in the formulas (1) and (3), R₂ be a substitutedor unsubstituted alkyl group having 1 to 20 carbon atoms, a substitutedor unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, asubstituted or unsubstituted silyl group or a substituted orunsubstituted aryl group having 6 to 30 ring carbon atoms, and R₁ and R₃to R₈ be a hydrogen atom.

In another preferred embodiment, in the formulas (1) and (3), R₂ and R₆are a substituted or unsubstituted alkyl group having 1 to 20 carbonatoms, a substituted or unsubstituted cycloalkyl group having 3 to 10ring carbon atoms, a substituted or unsubstituted silyl group or asubstituted or unsubstituted aryl group having 6 to 30 ring carbonatoms, and R₁, R₃, R₄, R₅, R₇ and R₈ are a hydrogen atom.

The substituted or unsubstituted alkyl group having 1 to 20 carbon atomsof R₂ and R₆ is preferably an alkyl group having 1 to 6 carbon atoms.The substituted or unsubstituted silyl group of R₂ and R₆ is preferablya substituted or unsubstituted alkylsilyl group having 3 to 30 carbonatoms, with a substituted or unsubstituted alkylsilyl group having 3 to12 carbon atoms being more preferable.

In another preferred embodiment, in the formulas (1) and (3), R₁ to R₈are preferably a hydrogen atom.

In the formulas (2) to (4), X₁, X₂, X₃ and X₄ are preferably an oxygenatom.

In the formula (2), R₁₁ to R₁₇ are preferably a hydrogen atom.

In the formula (3), R₂₁ to R₂₇ and R₃₁ to R₃₇ are preferably a hydrogenatom.

In the formula (4), R₄₁ to R₄₈ are preferably a hydrogen atom.

In the formula (1), it is preferred that Ar₁ to Ar₄ other than theheterocyclic group represented by the formula (2) be an unsubstitutedaryl group having 6 to 30 ring carbon atoms.

In the formula (3), it is preferred that Ar₂ and Ar₄ be an aryl grouphaving 6 to 30 ring carbon atoms.

When Ar₁ to Ar₄ other than the heterocyclic group represented by theformula (2) are an unsubstituted aryl group having 6 to 30 ring carbonatoms, this aryl group is preferably a phenyl group, a naphthyl group, aphenanthryl group, a fluorenyl group, an anthracenyl group, a chrycenylgroup or a fluoranthenyl group. It is particularly preferred that it bea phenyl group, a naphthyl group, a phenanthryl group or a fluorenylgroup.

In another preferred embodiment, in the formula (1), it is preferredthat Ar₁ to Ar₄ other than the heterocyclic group represented by theformula (2) be an aryl group having 6 to 30 ring carbon atoms and havinga substituent.

In another preferred embodiment, in the formula (3), it is preferredthat Ar₂ and Ar₄ be an aryl group having 6 to 30 ring carbon atoms andhaving a substituent.

Preferred examples of the substituent include a halogen atom, an alkylgroup, a cycloalkyl group, a silyl group, an aryl group or a cyanogroup.

If Ar₁ to Ar₄ other than the heterocyclic group represented by theformula (2) is an aryl group having a substituent, this aryl group ispreferably a phenyl group.

In another preferred embodiment, in the formula (3), it is preferredthat Ar₂ and Ar₄ be a heterocyclic group represented by the followingformula (4):

In the formula (4), one of R₄₁ to R₄₈ is used for connection to thenitrogen atom, and the other substituents are independently a hydrogenatom, a halogen atom, a substituted or unsubstituted alkyl group having1 to 20 carbon atoms, a substituted or unsubstituted alkenyl grouphaving 2 to 20 carbon atoms, a substituted or unsubstituted alkynylgroup having 2 to 20 carbon atoms, a substituted or unsubstituted silylgroup, a cyano group, a substituted or unsubstituted aryl group having 6to 20 ring carbon atoms or a substituted or unsubstituted heterocyclicgroup having 5 to 20 ring atoms, adjacent substituents of R₄₁ to R₄₈ maybe bonded to form a saturated or unsaturated ring, and X₄ is an oxygenatom or a sulfur atom.

In the specification, the “ring carbon atoms” mean carbon atoms thatform a saturated ring, unsaturated ring or aromatic ring. The “ringatoms” mean carbon atoms and hetero atoms that form a hetero ring(including a saturated ring, unsaturated ring or aromatic ring).

In addition, as the substituent in the “substituted or unsubstituted . .. ”, an alkyl group, a substituted or unsubstituted silyl group, analkoxy group, an aryl group, an aryloxy group, an aralkyl group, acycloalkyl group, a heterocyclic group, a halogen atom, an alkyl halidegroup, a hydroxyl group, a nitro group, a cyano group, a carboxy groupor the like, which will be given later, can be given.

The “unsubstituted” means that a group is substituted with a hydrogenatom and the hydrogen atom of the invention includes light hydrogen,deuterium and tritium.

Each of the groups represented by R₁ to R₈, R₁₁ to R₁₇, R₂₁ to R₂₇, R₃₁to R₃₇, R₄₁ to R₄₈ and Ar₁ to Ar₄ in the formulas (1) to (4), and thesubstituent in “substituted or unsubstituted . . . ” will be mentionedbelow in detail.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl,n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-heptyl andn-octyl. The alkyl group may be a substituent obtained by combination ofan alkylene group and an aryl group or the like (a phenylmethyl group,2-phenylisopropyl group or the like, for example).

The group preferably has 1 to 10 carbon atoms and more preferably 1 to 6carbon atoms. Of these, methyl, ethyl, propyl, isopropyl, n-butyl,s-butyl, isobutyl, t-butyl, n-pentyl and n-hexyl are preferable.

As the substituted silyl group, an alkylsilyl group having 3 to 30carbon atoms, an arylsilyl group having 8 to 30 ring carbon atoms or thelike can be given. Examples thereof include a trimethylsilyl group, atriethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilylgroup, a propyldimethylsilyl group, a triisopropylsilyl group, atriphenylsilyl group, or the like can be given.

The alkoxy group is represented by —OY. Examples for Y include thoseexemplified above for the alkyl group. The alkoxy group is methoxy orethoxy, for example.

The alkenyl group and the alkynyl group mentioned as R₁₁ to R₁₇, R₂₁ toR₂₇, R₃₁ to R₃₇ and R₄₁ to R₄₈ are preferably a vinyl group and anethynyl group, respectively.

Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl,1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,3-phenanthryl, 4-phenanthryl, 9-phenanthryl, naphthacenyl, pyrenyl,chrysenyl, benzo[c]phenanthryl, benzo[g]chrysenyl, triphenylenyl,1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 9-fluorenyl,benzofluorenyl, dibenzofluorenyl, 2-biphenylyl, 3-biphenylyl,4-biphenylyl, terphenyl and fluoranthenyl.

The aryl group mentioned as R₁ to R₈ preferably has 6 to 20 ring carbonatoms and more preferably 6 to 12 ring carbon atoms. Phenyl, biphenyl,tolyl, xylyl and 1-naphthyl are particularly preferable among theabove-mentioned aryl groups.

The aryloxy group is represented by —OZ. Examples for Z include thosedescribed above for the aryl group or the examples of a monocyclic groupand a fused ring group mentioned later. The aryloxy group is phenoxy,for example.

The aralkyl group is represented by —Y—Z. Examples for Y includealkylene corresponding to those described above for the alkyl group.Examples for Z include those described above for the aryl group. Thearalkyl group is preferably an aralkyl group having 7 to 50 carbonatoms, wherein the aryl part has 6 to 49 (preferably 6 to 30, morepreferably 6 to 20, and particular preferably 6 to 12) carbon atoms, andthe alkyl part has 1 to 44 (preferably 1 to 30, more preferably 1 to 20,still more preferably 1 to 10, and particularly preferably 1 to 6)carbon atoms. For example, a benzyl group, phenylethyl group, or2-phenylpropane-2-yl group can be given.

Examples of the cycloalkyl group include cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, 4-methylcyclohexyl, adamantyl and norbornyl.The cycloalkyl group has preferably 3 to 10, further preferably 3 to 8,and particularly preferably 3 to 6 ring carbon atoms.

Examples of the heterocyclic group include pyrrolyl, pyrazinyl,pyridinyl, indolyl, isoindolyl, imidazolyl, furyl, benzofuranyl,isobenzofuranyl, 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl,4-dibenzofuranyl, 1-dibenzothiophenyl, 2-dibenzothiophenyl,3-dibenzothiophenyl, 4-dibenzothiophenyl, quinolyl, isoquinolyl,quinoxalinyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl,9-carbazolyl, phenantridinyl, acridinyl, phenanthrolinyl, phenazinyl,phenothiazinyl, phenoxazinyl, oxazolyl, oxadiazolyl, furazanyl, thienyland benzothiophenyl.

The above-mentioned heterocyclic group preferably has 5 to 20 ring atomsand more preferably 5 to 14 ring atoms.

1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl, 4-dibenzofuranyl,1-dibenzothiophenyl, 2-dibenzothiophenyl, 3-dibenzothiophenyl,4-dibenzothiophenyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl,4-carbazolyl and 9-carbazolyl are preferable.

As the halogen atom, fluorine, chlorine, bromine and iodine can begiven. Fluorine is preferable.

As the alkyl halide group, a fluoromethyl group, a difluoromethyl group,a trifluoromethyl group, a fluoroethyl group, a trifluoromethyl group,or the like can be given.

Specific examples of the aromatic amine derivative are given below.

The above-mentioned aromatic amine derivatives can be used as anemitting material for an organic electroluminescence device. It can beused as a dopant, for example.

The organic electroluminescence device of the invention comprises one ormore organic thin film layers comprising an emitting layer between ananode and a cathode, wherein at least one layer of the organic thin filmlayers comprises the above-mentioned aromatic amine derivative singly oras a component of a mixture.

It is preferred that the emitting layer comprise the aromatic aminederivative. The emitting layer may be formed only of the aromatic aminederivative or may contain the aromatic amine derivative as a host or adopant.

In the organic electroluminescence device of the invention, it ispreferred that at least one layer of the organic thin film layerscontain the above-mentioned aromatic amine derivative and at least oneof an anthracene derivative represented by the following formula (5) anda pyrene derivative represented by the following formula (6). It ispreferred that the emitting layer contain the aromatic amine derivativeas a dopant and the anthracene derivative as a host.

(Anthracene Derivative)

The anthracene derivative represented by the formula (5) is thefollowing compound.

In the formula (5), Ar¹¹ and Ar¹² are independently a substituted orunsubstituted monocyclic group having 5 to 50 ring atoms, a substitutedor unsubstituted fused ring group having 8 to 50 ring atoms, or a groupformed by combination of a monocyclic group and a fused ring group andR¹⁰¹ to R¹⁰⁸ are independently a group selected from a hydrogen atom, asubstituted or unsubstituted monocyclic group having 5 to 50 ring atoms,a substituted or unsubstituted fused ring group having 8 to 50 ringatoms, a group formed by combination of a monocyclic group and a fusedring group, a substituted or unsubstituted alkyl group having 1 to 50carbon atoms, a substituted or unsubstituted cycloalkyl group having 3to 50 ring carbon atoms, a substituted or unsubstituted alkoxy grouphaving 1 to 50 carbon atoms, a substituted or unsubstituted aralkylgroup having 7 to 50 carbon atoms, a substituted or unsubstitutedaryloxy group having 6 to 50 ring carbon atoms, a substituted orunsubstituted silyl group, a halogen atom and a cyano group.

The monocyclic group in the formula (5) means a group which is composedonly of ring structures having no fused structure.

As specific examples of the monocyclic group having 5 to 50 (preferably5 to 30, more preferably 5 to 20) ring atoms, aromatic groups such as aphenyl group, biphenyl group, terphenyl group and quaterphenyl group,and heterocyclic groups such as a pyridyl group, pyradyl group,pyrimidyl group, triadinyl group, furyl group and thienyl group, can begiven preferably.

Among these, a phenyl group, biphenyl group or terphenyl group ispreferable.

The fused ring group in the formula (5) means a group formed by fusionof 2 or more ring structures.

As specific examples of the fused ring group having 8 to 50 (preferably8 to 30, more preferably 8 to 20) ring atoms, fused aromatic ring groupssuch as a naphthyl group, phenanthryl group, anthryl group, chrysenylgroup, benzanthryl group, benzophenanthryl group, triphenylenyl group,benzochrysenyl group, indenyl group, fluorenyl group,9,9-dimethylfluorenyl group, benzofluorenyl group, dibenzofluorenylgroup, fluoranthenyl group and benzofluoranthenyl group, and fusedheterocyclic groups such as a benzofuranyl group, benzothiophenyl group,indolyl group, dibenzofuranyl group, dibenzothiophenyl group, carbazolylgroup, quinolyl group and phenanthrolinyl group, can be givenpreferably.

Among these, a naphthyl group, phenanthryl group, anthryl group,9,9-dimethylfluorenyl group, fluoranthenyl group, benzanthryl group,dibenzothiophenyl group, dibenzofuranyl group or carbazolyl group ispreferable.

Specific examples of the alkyl group, silyl group, alkoxy group, aryloxygroup, aralkyl group, cycloalkyl group and halogen atom in the formula(5) are the same as the specific examples of the group represented by R₁to R₈, R₁₁ to R₁₇, R₂₁ to R₂₇, R₃₁ to R₃₇, R₄₁ to R₄₈ and Ar₁ to Ar₄ inthe formulas (1) to (4) and the specific examples of the substituent ofthe “substituted or unsubstituted . . . ”. Only preferable specificexamples in the formula (5) are given below.

As preferable substituents of “substituted or unsubstituted . . . ” inAr¹¹, Ar¹², and R¹⁰¹ to R¹⁰⁸, a monocyclic group, fused ring group,alkyl group, cycloalkyl group, silyl group, alkoxy group, cyano groupand halogen atom (in particular, fluorine) can be given. A monocyclicgroup and fused ring group are particularly preferable. The preferablespecific substituents are the same as those described in the formula (5)and those described in the formulas (1) to (4).

It is preferred that the anthracene derivative represented by theformula (5) be any of the following anthracene derivatives (A), (B) and(C), which is selected depending on the constitution or demandedproperties of an organic EL device to which it is applied.

(Anthracene Derivative (A))

This anthracene derivative is derivatives of the formula (5) whereinAr¹¹ and Ar¹² are independently a substituted or unsubstituted fusedring group having 8 to 50 ring atoms. This anthracene derivative can beclassified into the case that Ar¹¹ and Ar¹² are the same substituted orunsubstituted fused ring group and the case that Ar¹¹ and Ar¹² aredifferent substituted or unsubstituted fused ring groups.

Particularly preferred is the anthracene derivative of the formula (5)wherein Ar¹¹ and Ar¹² are different (including difference in substitutedpositions) substituted or unsubstituted fused ring groups. Preferablespecific examples of the fused ring are the same as those describedabove. Among those, a naphthyl group, phenanthryl group, benzanthrylgroup, 9,9-dimethylfluorenyl group and dibenzofuranyl group arepreferable.

(Anthracene Derivative (B))

This anthracene derivative is derivatives of the formula (5) wherein oneof Ar¹¹ and Ar¹² is a substituted or unsubstituted monocyclic grouphaving 5 to 50 ring atoms, and the other is a substituted orunsubstituted fused ring group having 8 to 50 ring atoms.

As a preferred embodiment, Ar¹² is a naphthyl group, phenanthryl group,benzanthryl group, 9,9-dimethylfluorenyl group or dibenzofuranyl group,and Ar¹¹ is a phenyl group substituted by a monocyclic group or fusedring group.

Preferable specific examples of the monocyclic group and fused ringgroup are the same as those described above.

As another preferred embodiment, Ar¹² is a fused ring group, and A¹¹ isan unsubstituted phenyl group. In this case, as the fused ring group, aphenanthryl group, 9,9-dimethylfluorenyl group, dibenzofuranyl group andbenzoanthryl group are particularly preferable.

(Anthracene Derivative (C))

This anthracene derivative is derivatives of formula (5) wherein Ar¹¹and Ar¹² are independently a substituted or unsubstituted monocyclicgroup having 5 to 50 ring atoms.

As a preferred embodiment, both Ar¹¹ and Ar¹² are a substituted orunsubstituted phenyl group.

As a further preferred embodiment, Ar¹¹ is an unsubstituted phenylgroup, and Ar¹² is a phenyl group having a monocyclic group or a fusedring group as a substituent, and Ar¹¹ and Ar¹² are independently aphenyl group having a monocyclic group or a fused ring group as asubstituent.

The preferable specific examples of the monocyclic group and fused ringgroup as a substituent are the same as those described above. As themonocyclic group as a substituent, a phenyl group and biphenyl group arefurther preferable. As the fused ring group as a substituent, a naphthylgroup, phenanthryl group, 9,9-dimethylfluorenyl group, dibenzofuranylgroup and benzanthryl group are further preferable.

Specific examples of the anthracene derivatives represented by theformula (5) are given below.

In another embodiment, the organic electroluminescence device may be adevice in which at least one of the organic thin film layers comprisesthe aromatic amine derivative represented by the above formula (1) and apyrene derivative represented by the following formula (6). It is morepreferred that the emitting layer contain the aromatic amine derivativeas a dopant and contain the pyrene derivative as a host.

In the formula (6), Ar¹¹¹ and Ar²²² are independently a substituted orunsubstituted aryl group having 6 to 30 ring carbon atoms;

L¹ and L² are independently a substituted or unsubstituted divalent arylgroup having 6 to 30 ring carbon atoms or a heterocyclic group;

m is an integer of 0 to 1, n is an integer of 1 to 4, s is an integer of0 to 1, and t is an integer of 0 to 3; and

L¹ or Ar¹¹¹ bonds to any position of the 1^(st) to 5^(th) positions ofpyrene, and L² or Ar²²² bonds to any position of the 6^(th) to 10^(th)positions of pyrene.

L¹ and L² in the formula (6) are preferably a divalent aryl groupcomposed of a substituted or unsubstituted phenylene group, asubstituted or unsubstituted biphenylene group, a substituted orunsubstituted naphthylene group, a substituted or unsubstitutedterphenylene group, a substituted or unsubstituted fluorenylene group,or a combination of these substituents.

These substituents are the same as those of the “substituted orunsubstituted . . . ” described above in the formulas (1) to (4). Thesubstituents of L¹ and L² are preferably an alkyl group having 1 to 20carbon atoms.

m in the formula (6) is preferably an integer of 0 to 1, and n in theformula (6) is preferably an integer of 1 to 2. s in the formula (6) ispreferably an integer of 0 to 1.

t in the formula (6) is preferably an integer of 0 to 2.

The aryl groups of Ar¹¹¹ and Ar²²² are the same as those described inthe formulas (1) to (4).

Preferable aryl groups are a substituted or unsubstituted aryl grouphaving 6 to 20 ring carbon atoms, with a substituted or unsubstitutedaryl group having 6 to 16 ring carbon atoms being more preferable.Preferable specific examples of the aryl groups include a phenyl group,naphthyl group, phenanthryl group, fluorenyl group, biphenyl group,anthryl group and pyrenyl group.

When the aromatic amine derivative is contained as a dopent, the amountthereof is preferably 0.1 to 20 mass %, more preferably 1 to 10 mass %.

The aromatic amine derivative and the anthracene derivative or thepyrene derivative may be used in a hole-injecting layer, ahole-transporting layer, an electron-injecting layer, and anelectron-transporting layer in addition to an emitting layer.

In the invention, as the organic EL device in which the organic thinfilm layer is composed of plural layers, one in which an anode, ahole-injecting layer, an emitting layer and a cathode are sequentiallystacked (anode/hole-injecting layer/emitting layer/cathode), one inwhich an anode, an emitting layer, an electron-injecting layer and acathode are sequentially stacked (anode/emittinglayer/electron-injecting layer/cathode), one in which an anode, ahole-injecting layer, an emitting layer, an electron-injecting layer anda cathode are sequentially stacked (anode/hole-injecting layer/emittinglayer/electron-injecting layer/cathode), one in which an anode, ahole-injecting layer, a hole-transporting layer, an emitting layer, anelectron-injecting layer and a cathode are sequentially stacked(anode/hole-injecting layer/hole-transporting layer/emittinglayer/electron-injecting layer/cathode) or the like can be given.

By allowing the organic thin film layer to be composed of plural layers,the organic EL device can be prevented from lowering of luminance orlifetime due to quenching. If necessary, an emitting material, a dopingmaterial, a hole-injecting material or an electron-injecting materialcan be used in combination. Further, due to the use of a dopingmaterial, luminance or luminous efficiency may be improved. Thehole-injecting layer, the emitting layer and the electron-injectinglayer may respectively be formed of two or more layers. In such case, inthe hole-injecting layer, a layer which injects holes from an electrodeis referred to as a hole-injecting layer, and a layer which receivesholes from the hole-injecting layer and transports the holes to theemitting layer is referred to as a hole-transporting layer. Similarly,in the electron-injecting layer, a layer which injects electrons from anelectrode is referred to as an electron-injecting layer and a layerwhich receives electrons from an electron-injecting layer and transportsthe electrons to the emitting layer is referred to as anelectron-transporting layer. Each of these layers is selected and usedaccording to each of the factors of a material, i.e. the energy level,heat resistance, adhesiveness to the organic layer or the metalelectrode or the like.

Examples of the material other than those represented by the formula (5)which can be used in the emitting layer together with the aromatic aminederivative of the invention include, though not limited thereto, fusedpolycyclic aromatic compounds such as naphthalene, phenanthrene,rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene,coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene,fluorene, spirofluorene and derivatives thereof, organic metal complexessuch as tris(8-quinolinolate)aluminum, triarylamine derivatives,styrylamine derivatives, stilbene derivatives, coumarin derivatives,pyrane derivatives, oxazone derivatives, benzothiazole derivatives,benzoxazole derivatives, benzimidazole derivatives, pyrazinederivatives, cinnamate derivatives, diketo-pyrrolo-pyrrole derivatives,acrylidone derivatives and quinacrylidone derivatives.

As the hole-injecting material, a compound which can transport holes,exhibits hole-injecting effects from the anode and excellenthole-injection effect for the emitting layer or the emitting material,and has an excellent capability of forming a thin film is preferable.Specific examples thereof include, though not limited thereto,phthalocyanine derivatives, naphthalocyanine derivatives, porphylinederivatives, benzidine-type triphenylamine, diamine-type triphenylamine,hexacyanohexaazatriphenylene, derivatives thereof, and polymer materialssuch as polyvinylcarbazole, polysilane and conductive polymers.

Of the hole-injecting materials usable in the organic EL device of theinvention, further effective hole-injecting materials are phthalocyaninederivatives.

Examples of the phthalocyanine (Pc) derivative include, though notlimited thereto, phthalocyanine derivatives such as H₂Pc, CuPc, CoPc,NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl₂SiPc,(HO)AlPc, (HO)GaPc, VOPc, TiOPc, MoOPc and GaPc-O-GaPc, andnaphthalocyanine derivatives.

In addition, it is also possible to sensitize carriers by adding to thehole-injecting material an electron-accepting substance such as a TCNQderivative.

Preferable hole-transporting materials usable in the organic EL deviceof the invention are aromatic tertiary amine derivatives.

Examples of the aromatic tertiary amine derivative include, though notlimited thereto,N,N′-diphenyl-N,N′-dinaphthyl-1,1′-biphenyl-4,4′-diamine,N,N,N′,N′-tetrabiphenyl-1,1′-biphenyl-4,4′-diamine or an oligomer or apolymer having these aromatic tertiary amine skeleton.

As the electron-injecting material, a compound which can transportelectrons, exhibits electron-injecting effects from the cathode andexcellent electron-injection effect for the emitting layer or theemitting material, and has an excellent capability of forming a thinfilm is preferable.

In the organic EL device of the invention, further effectiveelectron-injecting materials are a metal complex compound and anitrogen-containing heterocyclic derivative.

Examples of the metal complex compound include, though not limitedthereto, 8-hydroxyquinolinate lithium, bis(8-hydroxyquinolinate)zinc,tris(8-hydroxyquinolinate)aluminum, tris(8-hydroxyquinolinate)gallium,bis(10-hydroxybenzo[h]quinolinate)beryllium andbis(10-hydroxybenzo[h]quinolinate)zinc.

As examples of the nitrogen-containing heterocyclic derivative, oxazole,thiazole, oxadiazole, thiadiazole, triazole, pyridine, pyrimidine,triazine, phenanthroline, benzoimidazole, imidazopyridine or the likeare preferable, for example. Of these, a benzimidazole derivative, aphenanthroline derivative and an imidazopyridine derivative arepreferable.

As a preferred embodiment, a dopant is further contained in theseelectron-injecting materials, and in order to facilitate receivingelectrons from the cathode, it is further preferable to dope thevicinity of the cathode interface of the second organic layer with adopant, the representative example of which is an alkali metal.

As the dopant, a donating metal, a donating metal compound and adonating metal complex can be given. These reducing dopants may be usedsingly or in combination of two or more.

In the organic EL device of the invention, the emitting layer maycontain, in addition to at least one of the above-mentioned aromaticamine derivatives represented by the formula (1), at least one of anemitting material, a doping material, a hole-injecting material, ahole-transporting material and an electron-injecting material in thesame layer. Moreover, for improving stability of the organic EL deviceobtained by the invention to temperature, humidity, atmosphere, etc. itis also possible to prepare a protective layer on the surface of thedevice, and it is also possible to protect the entire device by applyingsilicone oil, resin, etc.

As the conductive material used in the anode of the organic EL device ofthe invention, a conductive material having a work function of more than4 eV is suitable. Carbon, aluminum, vanadium, iron, cobalt, nickel,tungsten, silver, gold, platinum, palladium or the like, alloys thereof,oxidized metals which are used in an ITO substrate and a NESA substratesuch as tin oxide and indium oxide and organic conductive resins such aspolythiophene and polypyrrole are used. As the conductive material usedin the cathode, a conductive material having a work function of smallerthan 4 eV is suitable. Magnesium, calcium, tin, lead, titanium, yttrium,lithium, ruthenium, manganese, aluminum, and lithium fluoride or thelike, and alloys thereof are used, but not limited thereto.Representative examples of the alloys include, though not limitedthereto, magnesium/silver alloys, magnesium/indium alloys andlithium/aluminum alloys. The amount ratio of the alloy is controlled bythe temperature of the deposition source, atmosphere, vacuum degree orthe like, and an appropriate ratio is selected. If necessary, the anodeand the cathode each may be composed of two or more layers.

In the organic EL device of the invention, in order to allow it to emitlight efficiently, it is preferred that at least one of the surfaces befully transparent in the emission wavelength region of the device. Inaddition, it is preferred that the substrate also be transparent. Thetransparent electrode is set such that predetermined transparency can beensured by a method such as deposition or sputtering by using theabove-mentioned conductive materials. It is preferred that the electrodeon the emitting surface have a light transmittance of 10% or more.Although no specific restrictions are imposed on the substrate as longas it has mechanical and thermal strength and transparency, a glasssubstrate and a transparent resin film can be given.

Each layer of the organic EL device of the invention can be formed by adry film-forming method such as vacuum vapor deposition, sputtering,plasma, ion plating or the like or a wet film-forming method such asspin coating, dipping, flow coating or the like. Although the filmthickness is not particularly limited, it is required to adjust the filmthickness to an appropriate value. If the film thickness is too large, alarge voltage is required to be applied in order to obtain a certainoptical output, which results in a poor efficiency. If the filmthickness is too small, pinholes or the like are generated, and asufficient luminance cannot be obtained even if an electrical field isapplied. The suitable film thickness is normally 5 nm to 10 μm, with arange of 10 nm to 0.2 μm being further preferable.

In the case of the wet film-forming method, a thin film is formed bydissolving or dispersing materials forming each layer in an appropriatesolvent such as ethanol, chloroform, tetrahydrofuran and dioxane. Any ofthe above-mentioned solvents can be used.

As the solution suitable for such wet film-forming method, it ispossible to use an organic EL material-containing solution whichcontains the aromatic amine derivative of the invention as an organic ELmaterial and a solvent.

It is preferred that the above-mentioned organic EL material contain ahost material and a dopant material, the dopant material be the aromaticamine derivative of the invention and the host material be at least oneselected from compounds represented by the formula (5).

In each organic thin film layer, an appropriate resin or additive may beused in order to improve film-forming properties, to prevent generationof pinholes in the film, or for other purposes.

The organic EL device of the invention can be suitably used as a planaremitting body such as a flat panel display of a wall-hanging television,backlight of a copier, a printer or a liquid crystal display, lightsources for instruments, a display panel, a navigation light, or thelike. The compound of the invention can be use not only in an organic ELdevice but also in the field of an electrophotographic photoreceptor, aphotoelectric converting element, a solar cell and an image sensor.

EXAMPLES Production Example 1

Aromatic amine derivative D-1 was produced as follows:

(1) Synthesis of Intermediate M1 (Reaction A)

In a stream of argon, 30.0 g of dibenzofuran and 300 mL of dehydratedtetrahydrofuran (THF) were put in a 1000 mL-recovery flask, and theresulting solution was cooled to −65° C. Then, 120 mL (1.65 M) of ahexane solution of n-butyllithium was added. The resulting mixture washeated gradually, and allowed to react at room temperature for 3 hours.After cooling to −65° C. again, 23.1 mL of 1,2-dibromoethane was addeddropwise thereto, and the reaction mixture was heated gradually and areaction was conducted for 3 hours at room temperature.

The reaction solution was separated and extracted by adding 2Nhydrochloric acid and ethyl acetate, and then the organic phase waswashed with clean water and saturated saline and dried with sodiumsulfate, and concentrated to obtain a crude product. The crude productwas purified with silica gel chromatography (methylene chloride), andsolids obtained were dried under reduced pressure to obtain 43.0 g ofwhite solids. The solids were identified as intermediate M1 by FD-MS(field desorption mass spectrometry) analysis.

(2) Synthesis of Intermediate M2 (Reaction B)

In a stream of argon, 11.7 g of intermediate M1, 10.7 mL of aniline,0.63 g of tris(dibenzylideneacetone)dipalladium(0) [Pd₂(dba)₃], 0.87 gof 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl [BINAP], 9.1 g of sodiumtert-butoxide and 131 mL of dehydrated toluene were put in a 300mL-recovery flask. A reaction was conducted at 85° C. for 6 hours.

After cooling, the reaction solution was filtered through cellite. Acrude product obtained was purified by silica gel column chromatography(n-hexane/methylene chloride (3/1)). Solids obtained were dried underreduced pressure to obtain 10.0 g of white solids. The solids wereidentified as intermediate M2 by FD-MS (field desorption massspectrometry) analysis.

(3) Synthesis of Compound D-1 (Reaction C)

In a stream of argon, 8.6 g of intermediate M2, 5.9 g of1,6-dibromo-3,8-diisopropylpyrene which had been synthesized by a knownmethod, 2.5 g of sodium tert-butoxide, 150 mg of palladium acetate (II)[Pd(OAc)₂], 135 mg of tri-tert-butylphosphine and 90 mL of dehydratedtoluene were put in a 300 mL-recovery flask. A reaction was conducted at85° C. for 7 hours.

The reaction solution was filtered, and a crude product obtained waspurified by silica gel chlormatography (toluene). Solids obtained wererecrystallized from toluene, and solids obtained were dried underreduced pressure, whereby 9.3 g of yellowish white solids were obtained.Analysis by FD-MS (field disorption mass spectrometery) was conductedfor the compound obtained. The UV absorption maximum wavelength λmax andthe flurescence emission maximum wavelength λmax in the toluene solutionare given below.

FDMS, calcd for C₅₈H₄₄N₂O₂=800. found m/z=(M+).

UV(PhMe); λmax=419 nm, FL(PhMe, λex=390 nm); λmax=452 nm

Production Example 2

Aromatic amine derivative D-2 was produced as follows:

(1) Synthesis of Intermediate M3 (Reaction B)

An intermediate was synthesized in the same manner as in the synthesisof intermediate M2, except that 4-isopropylaniline was used instead ofaniline. The intermediate obtained was identified as intermediate M3 byFD-MS (field desorption mass spectrometry) analysis.

(2) Synthesis of Compound D-2 (Reaction C)

A compound was synthesized in the same manner as in the synthesis ofcompound D-1, except that intermediate M3 was used instead ofintermediate M2. Analysis by FD-MS (field disorption mass spectrometery)was conducted for the compound obtained. The UV absorption maximumwavelength λmax and the flurescence emission maximum wavelength in thetoluene solution are given below.

FDMS, calcd for C₆₄H₅₆N₂O₂=884. found m/z=884 (M+).

UV(PhMe); λmax=425 nm, FL(PhMe, λex=400 nm); λmax=457 nm

Production Example 3

Aromatic amine derivative D-3 was produced as follows:

(1) Synthesis of Intermediate M4 (Reaction D)

In a stream of argon, 18.7 g of intermediate M1, 3.4 g of acetoamide,0.81 of copper iodide (I), 15.7 g of potassium carbonate and 90 mL ofxylene were put in a 300 mL-recovery flask. After stirring, 0.9 mL ofN,N′-dimethylethylenediamine was put, and a reaction was conducted at170° C. for 18 hours.

The reaction solution was filtered, and a crude product obtained waswashed with toluene, clean water and methanol. Solids obtained weredried under reduced pressure, whereby 8.2 g of solids were obtained. Thesolids obtained were identified as intermediate M4 by FD-MS (fielddesorption mass spectrometry) analysis.

(2) Synthesis of Intermediate M5 (Reaction E)

8.2 g of intermediate M4, 12.2 g of potassium hydroxide, 14 mL of cleanwater, 37 mL of toluene and 74 mL of ethanol were put in a 300mL-recovery flask. A reaction was conducted at 110° C. for 8 hours.

The reaction solution was separated and extracted by adding ethylacetate, and then the organic phase was washed with clean water andsaturated saline and dried with sodium sulfate, and concentrated toobtain a crude product. The crude product was purified with silica gelchromatography (ethyl acetate/hexane (1/1)), and solids obtained weredried under reduced pressure to obtain 6.6 g of white solids. The solidswere identified as intermediate M5 by FD-MS (field desorption massspectrometry) analysis.

(3) Synthesis of Intermediate M6 (Reaction B)

An intermediate was synthesized in the same manner as in the synthesisof intermediate M2, except that intermediate M5 was used instead ofaniline and 1-bromo-4-(trimethylsilyl)benzene was used instead ofintermediate M1. The intermediate obtained was identified asintermediate M6 by FD-MS (field desorption mass spectrometry) analysis.

(4) Synthesis of Compound D-3 (Reaction C)

A compound was synthesized in the same manner as in the synthesis ofD-1, except that intermediate M6 was used instead of intermediate M2.Analysis by FD-MS (field disorption mass spectrometery) was conductedfor the compound obtained. The UV absorption maximum wavelength λmax andthe flurescence emission maximum wavelength in the toluene solution aregiven below.

FDMS, calcd for C₆₄H₆₀N₂O₂Si₂=944. found m/z=944 (M+).

UV(PhMe); λmax=419 nm, FL(PhMe, λex=390 nm); λmax=452 nm

Production Example 4 Synthesis of Compound D-29 (Reaction C)

Aromatic amine derivative D-29 was produced as follows:

A compound was synthesized in the same manner as in the synthesis ofD-1, except that 1,6-dibromopyrene was used instead of1,6-dibromo-3,8-diisopropylpyrene. Analysis by FD-MS (field disorptionmass spectrometery) was conducted for the compound obtained. The UVabsorption maximum wavelength λmax and the flurescence emission maximumwavelength in the toluene solution are given below.

FDMS, calcd for C₅₂H₃₂N₂O₂=716. found m/z=716 (M+).

UV(PhMe); λmax=420 nm, FL(PhMe, λex=390 nm); λmax=449 nm

Production Example 5 Synthesis of Compound D-30 (Reaction C)

Aromatic amine derivative D-30 was produced as follows:

A compound was synthesized in the same manner as in the synthesis ofD-1, except that 1,6-dibromopyrene was used instead of1,6-dibromo-3,8-diisopropylpyrene and intermediate M3 was used insteadof intermediate M2. Analysis by FD-MS (field disorption massspectrometery) was conducted for the compound obtained. The UVabsorption maximum wavelength λmax and the flurescence emission maximumwavelength in the toluene solution are given below.

FDMS, calcd for C₅₈H₄₄N₂O₂=800. found m/z=800 (M+).

UV(PhMe); λmax=426 nm, FL(PhMe, λex=400 nm); λmax=455 nm

Production Example 6 Synthesis of Compound D-32

Aromatic amine derivative D-32 was produced as follows:

(1) Synthesis of Intermediate M7 (Reaction B)

An intermediate was synthesized in the same manner as in the synthesisof intermediate M2, except that intermediate M5 was used instead ofaniline. The intermediate obtained was identified as intermediate M7 byFD-MS (field desorption mass spectrometry) analysis.

(2) Synthesis of Compound D-32 (Reaction C)

A compound was synthesized in the same manner as in the synthesis ofD-1, except that intermediate M7 was used instead of intermediate M2.Analysis by FD-MS (field disorption mass spectrometery) was conductedfor the compound obtained. The UV absorption maximum wavelength λmax andthe flurescence emission maximum wavelength in the toluene solution aregiven below.

FDMS, calcd for C₇₀H₄₈N₂O₂=980. found m/z=980 (M+).

UV(PhMe); λmax=419 nm, FL(PhMe, λex=390 nm); λmax=448 nm

Production Example 7 Synthesis of Compound D-46

Aromatic amine derivative D-46 was produced as follows:

(1) Synthesis of Intermediate M8 (Reaction B)

An intermediate was synthesized in the same manner as in the synthesisof intermediate M2, except that 4-aminobenzonitrile was used instead ofaniline. The intermediate obtained was identified as intermediate M8 byFD-MS (field desorption mass spectrometry) analysis.

(2) Synthesis of Compound D-46 (Reaction C)

A compound was synthesized in the same manner as in the synthesis ofD-1, except that intermediate M8 was used instead of intermediate M2.Analysis by FD-MS (field disorption mass spectrometery) was conductedfor the compound obtained. The UV absorption maximum wavelength λmax andthe flurescence emission maximum wavelength in the toluene solution aregiven below.

FDMS, calcd for C₆₀H₄₂N₄O₂=850. found m/z=850 (M+).

UV(PhMe); λmax=398 nm, FL(PhMe, λex=370 nm); λmax=444 nm

Production Example 8 Synthesis of Compound D-53

Aromatic amine derivative D-53 was produced as follows.

(1) Synthesis of Intermediate M9 (Reaction B)

An intermediate was synthesized in the same manner as in the synthesisof intermediate M2, except that o-biphenylamine was used instead ofaniline. The intermediate obtained was identified as intermediate M9 byFD-MS (field desorption mass spectrometry) analysis.

(2) Synthesis of Compound D-53 (Reaction C)

A compound was synthesized in the same manner as in the synthesis ofD-1, except that intermediate M9 was used instead of intermediate M2 and1,6-dibromopyrene was used instead of 1,6-dibromo-3,8-diisopropylpyrene.Analysis by FD-MS (field disorption mass spectrometery) was conductedfor the compound obtained. The UV absorption maximum wavelength λmax andthe flurescence emission maximum wavelength in the toluene solution aregiven below.

FDMS, calcd for C₆₀H₄₀N₂O₂=868. found m/z=868 (M+).

UV(PhMe); λmax=429 nm, FL(PhMe, λex=400 nm); λmax=452 nm

Production Example 9 Synthesis of Compound D-54

Aromatic amine derivative D-54 was produced as follows:

(1) Synthesis of Intermediate M10 (Reaction B)

An intermediate was synthesized in the same manner as in the synthesisof intermediate M2, except that 4-amino-3-phenylbenzonitrile was usedinstead of aniline. The intermediate obtained was identified asintermediate M10 by FD-MS (field desorption mass spectrometry) analysis.

(2) Synthesis of Compound D-54 (Reaction C)

A compound was synthesized in the same manner as in the synthesis ofD-1, except hat 1,6-dibromopyrene was used instead of1,6-dibromo-3,8-diisopropylpyrene and intermediate M10 was used insteadof intermediate M2. Analysis by FD-MS (field disorption massspectrometery) was conducted for the compound obtained. The UVabsorption maximum wavelength λmax and the flurescence emission maximumwavelength in the toluene solution are given below.

FDMS, calcd for C₆₆H₃₈N₄O₂=918. found m/z=918 (M+).

UV(PhMe); λmax=424 nm, FL(PhMe, λex=400 nm); λmax=449 nm

Production Example 10 Synthesis of Compound D-68 (Reaction C)

Aromatic amine derivative D-68 was produced as follows:

A compound was synthesized in the same manner as in the synthesis ofD-1, except that intermediate M9 was used instead of intermediate M2.Analysis by FD-MS (field disorption mass spectrometery) was conductedfor the compound obtained. The UV absorption maximum wavelength λmax andthe flurescence emission maximum wavelength in the toluene solution aregiven below.

FDMS, calcd for C₇₀H₅₂N₂O₂=952. found m/z=952 (M+).

UV(PhMe); λmax=432 nm, FL(PhMe, λex=400 nm); λmax=456 nm

Production Example 11 Synthesis of Compound D-76

Aromatic amine derivative D-76 was produced as follows:

(1) Synthesis of Intermediate M11 (Reaction B)

An intermediate was synthesized in the same manner as in the synthesisof intermediate M2, except that intermediate M5 was used instead ofaniline and 1-bromonaphthalene was used instead of intermediate M1. Theintermediate obtained was identified as intermediate M11 by FD-MS (fielddesorption mass spectrometry) analysis.

(2) Synthesis of Compound D-76 (Reaction C)

A compound was synthesized in the same manner as in the synthesis ofD-1, except that intermediate M11 was used instead of intermediate M2.Analysis by FD-MS (field disorption mass spectrometery) was conductedfor the compound obtained. The UV absorption maximum wavelength λmax andthe flurescence emission maximum wavelength in the toluene solution aregiven below.

FDMS, calcd for C₆₆H₄₈N₂O₂=900. found m/z=900 (M+).

UV(PhMe); λmax=424 nm, FL(PhMe, λex=400 nm); λmax=451 nm

Production Example 12 Synthesis of Compound D-81 (Reaction C)

Aromatic amine derivative D-81 was produced as follows:

A compound was synthesized in the same manner as in the synthesis ofD-1, except that 1,6-dibromo-3,8-dicyclopropylpyrene was used instead of1,6-dibromo-3,8-diisopropylpyrene. Analysis by FD-MS (field disorptionmass spectrometery) was conducted for the compound obtained. The UVabsorption maximum wavelength λmax and the flurescence emission maximumwavelength in the toluene solution are given below.

FDMS, calcd for C₅₈H₄₀N₂O₂=796. found m/z=796 (M+).

UV(PhMe); λmax=426 nm, FL(PhMe, λex=400 nm); λmax=457 nm

Production Example 13 Synthesis of Compound D-83 (Reaction C)

Aromatic amine derivative D-83 was produced as follows:

A compound was synthesized in the same manner as in the synthesis ofD-1, except that 1,6-dibromo-3,8-dicyclopentylpyrene was used instead of1,6-dibromo-3,8-diisopropylpyrene. Analysis by FD-MS (field disorptionmass spectrometery) was conducted for the compound obtained. The UVabsorption maximum wavelength λmax and the flurescence emission maximumwavelength in the toluene solution are given below.

FDMS, calcd for C₆₂H₄₈N₂O₂=852. found m/z=852 (M+).

UV(PhMe); λmax=420 nm, FL(PhMe, λex=390 nm); λmax=453 nm

Production Example 14 Synthesis of Compound D-88 (Reaction C)

Aromatic amine derivative D-88 was produced as follows:

A compound was synthesized in the same manner as in the synthesis ofD-1, except that 1,6-dibromo-3,8-dicyclopentylpyrene was used instead of1,6-dibromo-3,8-diisopropylpyrene and intermediate M6 was used insteadof intermediate M2. Analysis by FD-MS (field disorption massspectrometery) was conducted for the compound obtained. The UVabsorption maximum wavelength λmax and the flurescence emission maximumwavelength in the toluene solution are given below.

FDMS, calcd for C₆₈H₆₄N₂O₂Si₂=996. found m/z=996 (M+).

UV(PhMe); λmax=419 nm, FL(PhMe, λex=390 nm); λmax=453 nm

Production Example 15 Synthesis of Compound D-89 (Reaction C)

Aromatic amine derivative D-89 was produced as follows:

A compound was synthesized in the same manner as in the synthesis ofD-1, except that 1,6-dibromo-3,8-dicyclobutylpyrene was used instead of1,6-dibromo-3,8-diisopropylpyrene. Analysis by FD-MS (field disorptionmass spectrometery) was conducted for the compound obtained. The UVabsorption maximum wavelength λmax and the flurescence emission maximumwavelength in the toluene solution are given below.

FDMS, calcd for C₆₀H₄₄N₂O₂=824. found m/z=824 (M+).

UV(PhMe); λmax=425 nm, FL(PhMe, λex=400 nm); λmax=456 nm

Production Example 16 Synthesis of Compound D-90 (Reaction C)

Aromatic amine derivative D-90 was produced as follows:

A compound was synthesized in the same manner as in the synthesis ofD-1, except that 1,6-dibromo-3,8-di-m-tolylpyrene was used instead of1,6-dibromo-3,8-diisopropylpyrene. Analysis by FD-MS (field disorptionmass spectrometery) was conducted for the compound obtained. The UVabsorption maximum wavelength λmax and the flurescence emission maximumwavelength in the toluene solution are given below.

FDMS, calcd for C₆₆H₄₄N₂O₂=896. found m/z=896 (M+).

UV(PhMe); λmax=432 nm, FL(PhMe, λex=400 nm); λmax=468 nm

Production Example 17 Synthesis of Compound D-96

Aromatic amine derivative D-96 was produced as follows:

(1) Synthesis of Intermediate M12 (Reaction A)

An intermediate was synthesized in the same manner as in the synthesisof intermediate M1, except that dibenzothiophene was used instead ofdibenzofuran. The intermediate obtained was identified as intermediateM12 by FD-MS (field desorption mass spectrometry) analysis.

(2) Synthesis of Intermediate M13 (Reaction B)

An intermediate was synthesized in the same manner as in the synthesisof intermediate M2, except that intermediate M12 was used instead ofintermediate M1. The intermediate obtained was identified asintermediate M13 by FD-MS (field desorption mass spectrometry) analysis.

(3) Synthesis of Compound D-96 (Reaction C)

A compound was synthesized in the same manner as in the synthesis ofD-1, except that 1,6-dibromopyrene was used instead of1,6-dibromo-3,8-diisopropylpyrene and intermediate M13 was used insteadof intermediate M2. Analysis by FD-MS (field disorption massspectrometery) was conducted for the compound obtained. The UVabsorption maximum wavelength λmax and the flurescence emission maximumwavelength in the toluene solution are given below.

FDMS, calcd for C₅₂H₃₂N₂S₂=748. found m/z=748 (M+).

UV(PhMe); λmax=423 nm, FL(PhMe, λex=400 nm); λmax=455 nm

In Examples 1 to 112 explained below, synthesis was conducted in thesame manner as in Production Examples 1 to 15 for compounds of which theproduction example is not given.

Example 1

On a glass substrate with a dimension of 25×75×1.1 mm, a 120 nm-thicktransparent electrode formed of indium tin oxide was provided. Thistransparent electrode functions as an anode. After subjecting toUV-ozone cleaning, the glass substrate was mounted in a vacuum vapordeposition apparatus.

First, a 60 nm-thick film formed ofN′,N″-bis[4-(diphenylamino)phenyl]-N′,N″-diphenylbiphenyl-4,4′-diaminewas deposited as a hole-injecting layer. Then, a 20 nm-thick film formedof N,N,N′,N′-tetrakis(4-biphenyl)-4,4′-benzidine was deposited thereonas a hole-transporting layer. Subsequently, anthracene derivative EM2 asa host material and aromatic amine derivative D-1 as a doping materialwere co-deposited in a mass ratio of 40:2 to form a 40 nm-thick emittinglayer.

Next, as an electron-injecting layer, a 20 nm-thick film formed oftris(8-hydroxyquinolinato)aluminum was deposited on this emitting layer.

Then, a 1 nm-thick film formed of lithium fluoride was deposited, and a150 nm-thick film formed of aluminum was deposited, whereby an organicEL device was fabricated. The aluminum/lithium fluoride layer functionsas a cathode.

For the organic EL device thus obtained, device performance (luminousefficiency) at a current density of 10 mA/cm² and the 1931 CIE (x,y)chromaticity coordinates were measured by the following methods. Theresults are shown in Table 1.

Luminance: Measured by means of a spectroradiometer (CS-1000,manufactured by Konica Minolta Holdings, Inc.).The 1931 CIE (x,y) chromaticity coordinates: Measured by means of aspectroradiometer (CS-1000, manufactured by Konica Minolta Holdings,Inc.).Luminous efficiency (L/J): L/J is the ratio of luminance to currentdensity. Current and voltage were measured by means of SOURCE MEASUREUNIT 236 (manufactured by Keithley Instruments Inc.) and luminance wasmeasured by means of a spectroradiometer. Current density was calculatedbased on a current value and an emission area, whereby L/J was obtained.Luminous efficiency (Im/W) was obtained by the following formula.

Luminous efficiency(Im/W)=L/J/Voltage×Circular constant

Example 2

An organic EL device was fabricated and evaluated in the same manner asin Example 1, except that aromatic amine derivative D-2 was used insteadof aromatic amine derivative D-1. The results are shown in Table 1.

Example 3

An organic EL device was fabricated and evaluated in the same manner asin Example 1, except that aromatic amine derivative D-3 was used insteadof aromatic amine derivative D-1. The results are shown in Table 1.

Comparative Example 1

An organic EL device was fabricated and evaluated in the same manner asin Example 1, except that the following compound H-1 was used instead ofaromatic amine derivative D-1. The results are shown in Table 1.

TABLE 1 Example 1 Example 2 Example 3 Com. Ex. 1 Host material EM2 EM2EM2 EM2 Doping material D-1 D-2 D-3 H-1 Driving voltage (V) 6.0 5.8 5.96.1 CIEx 0.139 0.131 0.133 0.133 CIEy 0.112 0.143 0.120 0.186 Efficiency(lm/W) 4.0 4.2 3.9 3.2

From Table 1, it is apparent that, as compared with the known compoundH-1, the dibenzofuran derivative used in Examples contributed toimprovement in efficiency and a significant decrease in CIEy value(emitted at a significantly shorter wavelength). The reason therefor isassumed as follows. In the compound of the invention, in thedibenzofuranyl group or the dibenzothiophenyl group, a lone pair of thenitrogen atom exerts influence on the electron density of the aromaticring which is bonded to the nitrogen atom, and a lone pair of the oxygenatom or the sulfur atom exerts influence on the aromatic ring which isnot bonded to the nitrogen atom. As a result, electron-attractingeffects of the oxygen atom or the sulfur atom which has largerelectronegativity than that of a carbon atom are exhibited in thearomatic ring which is bonded to the nitrogen atom. Therefore, ascompared with a compound such as H-1 which has only an aromatichydrocarbon group, the compound of the invention allows an organic ELdevice to emit at a shorter wavelength.

Example 4

On a glass substrate with a dimension of 25×75×1.1 mm, a 120 nm-thicktransparent electrode formed of indium tin oxide was provided. Thistransparent electrode functions as an anode. After cleaning byirradiating UV rays and ozone, this substrate was mounted in a vacuumvapor deposition apparatus.

First, a 50 nm-thick film formed of HT-1 having the following structurewas deposited as a hole-injecting layer. Then, a 45 nm-thick film formedof N,N,N′,N′-tetrakis(4-biphenyl)-4,4′-benzidine was deposited thereon.Subsequently, anthracene derivative EM9 as a host material and aromaticamine derivative D-1 as a doping material were co-deposited in a massratio of 25:5 to form a 30 nm-thick emitting layer.

Next, as an electron-injecting layer, a 25 nm-thick film formed of ET-1having the following structure was deposited on this emitting layer.

Then, a 1 nm-thick film formed of lithium fluoride was deposited, and a150 nm-thick film formed of aluminum was deposited, whereby an organicEL device was fabricated. The aluminum/lithium fluoride layer functionsas a cathode.

The organic EL device thus obtained was evaluated in the same manner asin Example 1. The results are shown in Table 2.

Examples 5 to 42 and Comparative Example 2

Organic EL devices were fabricated and evaluated in the same manner asin Example 4, except that the host material and the doping material werechanged to those shown in Table 2. The results are shown in Table 2.

The external quantum yield was measured as follows:

Current with a current density of 10 mA/cm² was allowed to pass througheach of the organic EL devices thus obtained. Emission spectrum wasmeasured by means of a spectroradiometer (CS-1000, manufactured byKonica Minolta Holdings, Inc) and the external quantum yield wascalculated by the following expression (1):

$\begin{matrix}\begin{matrix}{{E.Q.E.} = {\frac{N_{P}}{N_{E}} \times 100}} \\{= {\frac{\frac{\left( {\pi/10^{9}} \right){\int{{\varphi (\lambda)} \cdot {\lambda}}}}{hc}}{\frac{J/10}{e}} \times 100}} \\{= {\frac{\frac{\left( {\pi/10^{9}} \right){\Sigma \left( {{\varphi (\lambda)} \cdot (\lambda)} \right)}}{hc}}{\frac{J/10}{e}} \times 100\mspace{11mu} (\%)}}\end{matrix} & {{Expression}\mspace{14mu} (1)}\end{matrix}$

N_(P): Number of photonsN_(E): Number of electronsπ: Circular constant=3.1416

λ: Wavelength (nm)

φ: Emission intensity (W/sr·m²·nm)h: Planck's constant=6.63×10⁻³⁴ (J·s)c: Speed of light=3×10⁸ (m/s)J: Current density (mA/cm²)e: Electric charge=1.6×10⁻¹⁹ (C)

TABLE 2 External quantum Host Doping yield Examples material materialCIEx CIEy (%)  4 EM9 D-1 0.136 0.100 6.3  5 EM13 D-1 0.136 0.103 7.3  6EM28 D-1 0.136 0.104 7.3  7 EM29 D-1 0.136 0.103 7.2  8 EM31 D-1 0.1360.105 7.3  9 EM32 D-1 0.136 0.105 7.2 10 EM69 D-1 0.136 0.104 6.8 11EM70 D-1 0.136 0.101 6.8 12 EM73 D-1 0.137 0.103 6.9 13 EM125 D-1 0.1370.106 6.5 14 EM133 D-1 0.137 0.107 6.5 15 EM364 D-1 0.139 0.118 6.2 16EM367 D-1 0.135 0.104 6.7 17 EM9 D-2 0.128 0.130 6.5 18 EM13 D-2 0.1280.133 7.2 19 EM28 D-2 0.128 0.134 7.2 20 EM29 D-2 0.128 0.133 7.1 21EM31 D-2 0.128 0.135 7.2 22 EM32 D-2 0.128 0.135 7.1 23 EM69 D-2 0.1280.134 6.9 24 EM70 D-2 0.128 0.131 6.8 25 EM73 D-2 0.129 0.133 6.8 26EM125 D-2 0.129 0.136 6.6 27 EM133 D-2 0.129 0.137 6.6 28 EM364 D-20.131 0.148 6.3 29 EM367 D-2 0.127 0.134 6.7 30 EM9 D-3 0.130 0.108 6.431 EM13 D-3 0.131 0.111 7.3 32 EM28 D-3 0.131 0.112 7.3 33 EM29 D-30.131 0.111 7.2 34 EM31 D-3 0.131 0.113 7.3 35 EM32 D-3 0.131 0.113 7.236 EM69 D-3 0.130 0.112 7.1 37 EM70 D-3 0.130 0.109 6.9 38 EM73 D-30.131 0.111 6.9 39 EM125 D-3 0.131 0.114 6.7 40 EM133 D-3 0.131 0.1156.7 41 EM364 D-3 0.133 0.126 6.3 42 EM367 D-3 0.130 0.112 6.7 Com. Ex. 2EM2 H-1 0.133 0.185 5.9

Examples 43 to 71 and Comparative Example 3

Organic EL devices were fabricated and evaluated in the same manner asin Example 1, except that the host material and the doping material werechanged to those shown in Table 3. The results are shown in Table 3.

The external quantum yield was measured by the same method as mentionedabove.

TABLE 3 External Host Doping Voltage quantum yield Examples materialmaterial (V) CIEx CIEy (%) 43 EM2 D-1 6.0 0.139 0.112 6.2 44 EM2 D-2 5.80.131 0.143 6.8 45 EM2 D-3 5.9 0.133 0.120 6.4 46 EM2 D-10 5.8 0.1340.151 6.9 47 EM2 D-16 5.8 0.135 0.158 6.7 48 EM2 D-17 6.1 0.135 0.1506.5 49 EM2 D-29 6.0 0.132 0.110 6.1 50 EM2 D-30 5.8 0.136 0.134 6.6 51EM2 D-32 6.1 0.131 0.110 6.0 52 EM2 D-35 5.9 0.133 0.135 6.7 53 EM2 D-365.9 0.133 0.121 6.5 54 EM2 D-37 6.1 0.132 0.140 6.5 55 EM2 D-38 6.00.138 0.114 6.2 56 EM2 D-42 6.0 0.130 0.129 6.8 57 EM2 D-46 5.8 0.1290.102 6.1 58 EM2 D-50 5.8 0.129 0.094 6.1 59 EM2 D-53 6.0 0.137 0.1256.7 60 EM2 D-54 6.0 0.137 0.122 6.9 61 EM2 D-59 6.1 0.132 0.093 5.9 62EM2 D-65 6.0 0.132 0.110 6.1 63 EM2 D-68 6.0 0.137 0.130 6.6 64 EM2 D-766.1 0.131 0.131 6.0 65 EM2 D-83 6.0 0.139 0.114 6.1 66 EM2 D-84 6.00.137 0.120 6.5 67 EM2 D-85 6.0 0.137 0.099 6.0 68 EM2 D-86 6.0 0.1300.125 6.8 69 EM2 D-88 6.0 0.139 0.114 6.3 70 EM2 D-90 5.7 0.139 0.1697.0 71 EM2 D-94 5.9 0.135 0.165 6.8 Com. Ex. 3 EM2 H-2 5.9 0.137 0.1804.1

Example 72

A glass substrate (GEOMATEC CO., LTD.) of 25 mm×75 mm×1.1 mm with an ITOtransparent electrode (anode) was subjected to ultrasonic cleaning withisopropyl alcohol for 5 minutes, and cleaned with ultraviolet rays andozone for 30 minutes. The resultant glass substrate with transparentelectrode lines was mounted on a substrate holder in a vacuum vapordeposition apparatus. First, compound A-1 shown below was formed into afilm in a thickness of 50 nm on the surface of the transparenceelectrode on which the transparence electrode lines were formed so as tocover the transparent electrode. Subsequent to the formation of the A-1film, compound A-2 shown below was formed thereon into a film in athickness of 45 nm.

Further, on this A-2 film, compound EM31 as a host material and compoundD-1 of the invention as a doping material were formed into a film in athickness of 25 nm with a film thickness ratio of 20:1, whereby a blueemitting layer was formed.

On this film, as an electron-transporting layer, ET-2 having thefollowing structure was formed into a 25 nm-thick film by deposition.Thereafter, LiF was formed into a 1 nm-thick film. Metal Al wasdeposited in a thickness of 150 nm as a metal cathode, therebyfabricating an organic EL device.

The resulting organic emitting device was evaluated in the same manneras in Example 1. The external quantum yield was measured by the samemethod as mentioned above. The results are shown in Table 4.

Examples 73 to 112 and Comparative Examples 4 and 5

Organic EL devices were fabricated and evaluated in the same manner asin Example 72, except that the host material and the doping materialwere changed to those shown in Table 4. The external quantum yield wasmeasured by the same method as mentioned above. The results are shown inTable 4.

TABLE 4 External Host Doping Voltage quantum yield Examples materialmaterial (V) CIEx CIEy (%) 72 EM31 D-1 3.6 0.138 0.095 8.0 73 EM31 D-23.5 0.138 0.120 8.2 74 EM31 D-29 3.6 0.137 0.093 7.6 75 EM31 D-30 3.50.139 0.108 7.8 76 EM31 D-38 3.6 0.138 0.100 7.9 77 EM31 D-42 3.6 0.1380.116 8.1 78 EM31 D-46 3.4 0.137 0.084 7.2 79 EM31 D-50 3.4 0.137 0.0807.0 80 EM31 D-53 3.6 0.138 0.100 8.1 81 EM31 D-54 3.5 0.138 0.098 7.8 82EM31 D-65 3.6 0.139 0.101 7.9 83 EM31 D-68 3.6 0.138 0.105 8.1 84 EM31D-83 3.5 0.137 0.102 8.0 85 EM31 D-85 3.6 0.137 0.102 7.9 86 EM31 D-863.6 0.138 0.114 8.1 87 EM31 D-90 3.4 0.140 0.159 7.7 88 EM116 D-1 3.60.137 0.090 7.4 89 EM116 D-2 3.6 0.138 0.110 7.8 90 EM116 D-29 3.7 0.1380.088 7.0 91 EM116 D-30 3.6 0.139 0.100 7.4 92 EM116 D-38 3.5 0.1380.096 7.5 93 EM116 D-42 3.6 0.138 0.102 7.5 94 EM116 D-46 3.7 0.1380.080 6.8 95 EM116 D-50 3.6 0.137 0.079 6.6 96 EM116 D-53 3.6 0.1370.097 7.4 97 EM116 D-54 3.7 0.138 0.090 7.4 98 EM116 D-65 3.6 0.1380.097 7.5 99 EM116 D-68 3.6 0.138 0.101 7.7 100 EM116 D-83 3.6 0.1380.096 7.5 101 EM116 D-85 3.7 0.139 0.095 7.4 102 EM116 D-86 3.6 0.1390.104 7.7 103 EM116 D-90 3.5 0.138 0.145 7.3 104 EM205 D-1 3.6 0.1380.096 8.1 105 EM205 D-2 3.6 0.137 0.122 8.2 106 EM205 D-46 3.5 0.1380.088 7.4 107 EM205 D-50 3.5 0.137 0.081 7.1 108 EM205 D-53 3.6 0.1380.100 8.2 109 EM205 D-54 3.6 0.138 0.100 8.0 110 EM205 D-68 3.6 0.1380.104 8.1 111 EM205 D-83 3.6 0.139 0.103 8.2 112 EMP1 D-1 3.2 0.1430.115 6.8 Com. Ex. 4 EMP1 H-2 3.2 0.143 0.201 5.8 Com. Ex. 5 EM31 H-23.6 0.137 0.178 5.2

From Tables 1 to 4, it can be understood that the devices of Examplesmaintained high efficiency and exhibited high color reproducibility. Asa result, the invention can realize a display device which exhibit highcolor reproducibility at low power consumption.

INDUSTRIAL APPLICABILITY

The organic EL device of the invention can be suitably used as a planaremitting body such as a flat panel display of a wall-hanging television,backlight of a copier, a printer, or a liquid crystal display, lightsources for instruments, a display panel, a navigation light, and thelike.

Although only some exemplary embodiments and/or examples of thisinvention have been described in detail above, those skilled in the artwill readily appreciate that many modifications are possible in theexemplary embodiments and/or examples without materially departing fromthe novel teachings and advantages of this invention. Accordingly, allsuch modifications are intended to be included within the scope of thisinvention.

The documents described in the specification are incorporated herein byreference in its entirety.

1. An organic electroluminescence device comprising one or more organicthin film layers comprising an emitting layer between an anode and acathode, wherein at least one layer of the organic thin film layerscomprises: an aromatic amine derivative represented by the followingformula (A1):

wherein R₁₀₁ to R₁₀₈ are independently a hydrogen atom, and Ar₁₀₁ toAr₁₀₄ are independently a group selected from the group consisting ofsubstituted or unsubstituted phenyl, substituted or unsubstitutednaphthyl, substituted or unsubstituted biphenylyl, substituted orunsubstituted terphenyl, 2-fluorenyl, 2-dibenzofuranyl,3-dibenzofuranyl, 4-dibenzofuranyl, 2-dibenzothiophenyl, pyridinyl andquinolyl, provided that at least one of Ar₁₀₁ to Ar₁₀₄ is a heterocyclicgroup represented by the following formula (A2):

wherein R₁₁₁ to R₁₁₇ are independently a hydrogen atom, or a groupselected from the group consisting of methyl, t-butyl, trimethylsilyland phenyl, adjacent substituents of R₁₁₁ to R₁₁₇ may be bonded to eachother to form a saturated or unsaturated ring, and X₁₀₁ is an oxygenatom or a sulfur atom; and an anthracene derivative represented by thefollowing formula (5):

wherein Ar¹¹ and Ar¹² are independently a substituted or unsubstitutedmonocyclic group having 5 to 50 ring atoms, a substituted orunsubstituted fused ring group having 8 to 50 ring atoms, or a groupformed by combination of the monocyclic group and the fused ring groupand R¹⁰¹ to R¹⁰⁸ are independently a group selected from a hydrogenatom, a substituted or unsubstituted monocyclic group having 5 to 50ring atoms, a substituted or unsubstituted fused ring group having 8 to50 ring atoms, a group formed by combination of the monocyclic group andthe fused ring group, a substituted or unsubstituted alkyl group having1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl grouphaving 3 to 50 ring carbon atoms, a substituted or unsubstituted alkoxygroup having 1 to 50 carbon atoms, a substituted or unsubstitutedaralkyl group having 7 to 50 carbon atoms, a substituted orunsubstituted aryloxy group having 6 to 50 ring carbon atoms, asubstituted or unsubstituted silyl group, a halogen atom and a cyanogroup.
 2. The organic electroluminescence device according to claim 1wherein in formula (5), Ar¹¹ and Ar¹² are independently a substituted orunsubstituted fused ring group having 10 to 50 ring carbon atoms.
 3. Theorganic electroluminescence device according to claim 1 wherein informula (5), one of Ar¹¹ and Ar¹² is a substituted or unsubstitutedmonocyclic group having 5 to 50 ring atoms, and the other is asubstituted or unsubstituted fused ring group having 10 to 50 ringatoms.
 4. The organic electroluminescence device according to claim 3wherein in formula (5), Ar¹² is a naphthyl group, a phenanthryl group, abenzanthryl group or a dibenzofuranyl group, and Ar¹¹ is a phenyl groupwhich is unsubstituted or substituted by a monocyclic group or fusedring group.
 5. The organic electroluminescence device according to claim3 wherein in formula (5), Ar¹² is a substituted or unsubstituted fusedring group having 8 to 50 ring atoms, and Ar¹¹ is an unsubstitutedphenyl group.
 6. The organic electroluminescence device according toclaim 1 wherein in formula (5), Ar¹¹ and Ar¹² are independently asubstituted or unsubstituted monocyclic group having 5 to 50 ring atoms.7. The organic electroluminescence device according to claim 6 whereinin formula (5), Ar¹¹ and Ar¹² are independently a substituted orunsubstituted phenyl group.
 8. The organic electroluminescence deviceaccording to claim 7 wherein in formula (5), Ar¹¹ is an unsubstitutedphenyl group and Ar¹² is a phenyl group having a monocyclic group or afused ring group as a substituent.
 9. The organic electroluminescencedevice according to claim 7 wherein in formula (5), Ar¹¹ and Ar¹² areindependently a phenyl group having a monocyclic group or a fused ringgroup as a substituent.
 10. The organic electroluminescence deviceaccording to claim 1, wherein the substituents for any substitutedgroups in the formula (A1) are independently selected from the groupconsisting of methyl, ethyl, isopropyl, 2,2-dimethylpropyl, t-butyl,trimethylsilyl, methoxy, phenyl, 2-phenylpropane-2-yl, cyclopentyl,cyclohexyl, fluorine, trifluoromethyl and cyano.
 11. An electronicequipment comprising the organic electroluminescence device according toclaim
 1. 12. The organic electroluminescence device according to claim1, wherein Ar₁₁ and Ar₁₂ are independently a phenyl group or naphthylgroup which is unsubstituted or substituted by a phenyl group ornaphthyl group.
 13. The organic electroluminescence device according toclaim 12, wherein Ar₁₁ is a phenyl group which is unsubstituted orsubstituted by a phenyl group or a naphthyl group, and Ar₁₂ is anaphthyl group which is unsubstituted or substituted by a phenyl groupor naphthyl group.
 14. The organic electroluminescence device accordingto claim 13, wherein Ar₁₂ is a naphthyl group substituted by a phenylgroup.
 15. The organic electroluminescence device according to claim 1,wherein Ar₁₁ and Ar₁₂ are independently a naphthyl group which isunsubstituted or substituted by a phenyl group or naphthyl group. 16.The organic electroluminescence device according to claim 1, whereinAr₁₀₁ to Ar₁₀₄ are independently a group selected from the groupconsisting of a phenyl group, a biphenyl group, a terphenyl group, a2-dibenzofuranyl group, a 3-dibenzofuranyl group, and a 4-dibenzofuranylgroup.